CN104132921A - Chemical vapor deposition based method for preparing surface Raman enhanced active substrate - Google Patents
Chemical vapor deposition based method for preparing surface Raman enhanced active substrate Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 62
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 95
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- 239000002245 particle Substances 0.000 claims description 11
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a chemical vapor deposition based method for preparing a surface Raman enhanced active substrate. The method comprises the following steps: covering a layer of silver membrane on the surface of a silicon sheet through a thermal evaporation method; placing the silicon sheet covered by a layer of silver nano membrane into a chemical vapor deposition (CVD) reaction cavity, heating to a preset temperature to remove water from the solid silver membrane so as to form silver nano particles; introducing a reaction gas into the cavity at the preset temperature to evenly grow a layer of silicon membrane on the surfaces of the silver nano particles so as to form a core-shell nano spherical array structure; then taking out the silicon sheet with a core-shell nano spherical array structure from the CVD reaction activity, and covering a layer of silver membrane with a preset thickness on the core-shell nano spherical array structure through a thermal evaporation method so as to obtain the surface Raman enhanced active substrate. The prepared active substrate has extremely high SERS enhancement and sensitivity, moreover, the preparation technology is simple, repeatability is good, and large-scale preparation can be achieved.
Description
Technical field
The present invention relates to nano material preparation and biochemistry detection analysis field, relate in particular to a kind of method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition.
Background technology
Raman scattering spectrum, due to its specificity to molecule and chemical bond vibration peak, becomes a powerful molecular detection technology.Due to the very little scattering xsect of Raman scattering, Raman scattering is a very weak process, and is unfavorable for the qualitative analysis of micro substance.Surface Raman enhancement scattering (SERS) effect refers to that the compound that is adsorbed on roughening metal surface is due to the surperficial local plasmon excimer caused Electromagnetic enhancement that is excited, and on rough surface, adsorb the chemistry that active site that molecular composition Raman strengthens causes and strengthen, cause adsorbing the phenomenon that the Raman scattering signal of molecule strengthens greatly than common Raman scattering (NRS) signal.Surface Raman enhancement has high sensitivity because of it, and the ability of fast detecting can obtain the structural information that conventional Raman spectrum is difficult to obtain, and is widely used in study of surfaces, biological surface science, the fields such as food security.
Surface Raman enhancement active substrate is generally used the noble metals such as silver, gold, copper as coarse metal surface." focus " that SERS effect is mainly derived from Electromagnetic enhancement in roughened metal surface (hotspot).At present a lot of about active substrate preparation method's bibliographical information, these methods mainly comprise the self assembly of metal colloid particles, reactive ion etching (RIE), electron beam lithography (EBL) and nanosphere etching etc.For commercialization, practical SERS active substrate, the repeatability of substrate, the homogeneity of Raman signal, the sensitivity of detection and the cost of preparation are all to need the factor considered.But the SERS active substrate that uses above-mentioned preparation method to prepare, has some limitation.For example, metal colloid particles is inevitably reunited in self assembling process, the poor reproducibility of SERS signal, thus limited large area preparation; And having good control based on lithographic technique (EBL and RIE) although to underlying structure, preparation cost is high, consuming time, and is difficult to prepare the SERS substrate of centimetre magnitude, is therefore difficult in practical application.In addition, based on lithographic technique, be difficult to prepare spacing in 10 nanometers and following nanostructured.In general, when the gap in noble metal substrate between nano unit is less than 10 nanometer, can there is very strong local coupling in this gap in electromagnetic wave, thereby produce obvious SERS effect.The auxiliary assembling of anodised aluminium (AA0) template metal Nano structure, prepares gap controlled (10 nanometer) although provide under a kind of relatively low cost condition, reproducible, the method for hypersensitive SERS substrate.But the method preparation process is loaded down with trivial details, technological means requires high, is difficult to prepare large area, the array of long-range order.Single PS (polystyrene) bead that disperses one deck densification in smooth substrates, coupled ion etching and metal plating, be also one of feasible method of preparation SERS active substrate.The method preparation is simple, with low cost, but sensitivity is relatively low, and PS bead is combined not firmly with substrate, under ultrasound condition, is easy to come off.
Summary of the invention
The embodiment of the present invention provides a kind of method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition, so that the active substrate of preparation has high SERS, strengthens and sensitivity, and preparation technology is simple, reproducible, can large area preparation.
In order to reach above-mentioned technical purpose, the embodiment of the present invention provides a kind of method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition, and the described method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition comprises:
At the hot evaporation one deck silver of silicon chip surface film;
Silicon chip after evaporation silver nanoparticle film is put into chemical vapor deposition CVD reaction chamber and be heated to preset temperature, make the solid-state dehumidification of described silver-colored film to form silver nano-grain;
Under described preset temperature, pass into reacting gas, make described silver nano-grain surface uniform silicon growth layer film, form the spherical array structure of core-shell nano;
The silicon chip that forms the spherical array structure of core-shell nano is taken out in described CVD reaction chamber, and the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtains surface Raman enhancement active substrate.
Preferably, in an embodiment of the present invention, described before the hot evaporation one deck silver of silicon chip surface film, described method can also comprise: the silicon chip of monocrystalline is used to acetone, ethanol, deionized water ultrasonic cleaning successively; Described silicon chip is single-sided polishing, the p-type of doping, N-shaped monocrystalline silicon piece or unadulterated intrinsic silicon chip.
Preferably, in an embodiment of the present invention, described monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, can comprise: utilize supersonic cleaning machine, ultrasonic power is 180W, frequency is 40KHz, and monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, and the ultrasonic cleaning time is respectively 10 minutes; Silicon chip after ultrasonic cleaning is put into the concentrated sulphuric acid and the hydrogen peroxide that volume ratio is 4:1 again and soak 15 minutes to remove oxide on surface, by washed with de-ionized water; Finally silicon chip is put into 5% hydrofluorite and soak 5 minutes, make silicon chip surface form Si-H key.
Preferably, in an embodiment of the present invention, described at the hot evaporation one deck silver of silicon chip surface film, can comprise: utilize thermal evaporation coating system at the hot evaporation one deck silver of silicon chip surface film, in hot evaporation chamber, pressure is evacuated to 2.5 * 10
-4Pa, the speed of hot evaporation is
the sample stage velocity of rotation at silicon chip place is 20r/min, and the thickness of metallic film is 15nm.
Preferably, in an embodiment of the present invention, the limit heating-up temperature of described reaction cavity is 1050 ℃, is deposited on the silver-colored film of described silicon chip surface in steady state (SS) under room temperature.When cavity being heated in preset temperature process, the silver-colored film in half stable state, in the diffusion of substrate surface generation atom, forms the granule of nanoscale to reduce total free energy.Due to the melt temperature of preset temperature well below metal, while forming nano particle metal in solid-state, the process that Here it is " solid-state dehumidification ".
Preferably, in an embodiment of the present invention, when thickness of metal film one timing, preset temperature is higher, and at this temperature, temperature retention time is longer, and the size of the metallic particles of formation is larger, and between particle, spacing is larger, and particle density is lower.
Preferably, in an embodiment of the present invention, described preset temperature is 540 ℃, and when the sample at described silicon chip place is heated to 540 ℃ in 30 minutes, described silver-colored film has formed silver nano-grain.
Preferably, in an embodiment of the present invention, in described reaction cavity, keep invariablenes pressure of liquid, in heating process, pass into hydrogen to go back the silver oxide of original surface.Pressure is fixed on 10Torr, and the flow of hydrogen is 40sccm.
Preferably, in an embodiment of the present invention, the described reacting gas passing under described preset temperature can comprise: silane SiH
4with hydrogen H
2; Utilize the sample at described silicon chip place to form on the basis of described silver nano-grain, maintain described preset temperature constant, in reaction chamber, pass into reacting gas, i.e. 5%SiH
4in H
2and the flow that regulates hydrogen is to maintain invariablenes pressure of liquid in chamber, the silicon atom that now under described preset temperature, thermal cracking silane obtains is deposited on the surface of Nano silver grain, makes described silver nano-grain surface uniform silicon growth layer film, forms the spherical array structure of core-shell nano; In above-mentioned course of reaction, reacting gas SiH
4flow be 20sccm, the flow of hydrogen is 20sccm, invariablenes pressure of liquid is at 10Torr, growth time is 90 minutes.
Preferably, in an embodiment of the present invention, the described silicon chip by the spherical array structure of formation core-shell nano takes out in described CVD reaction chamber, the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtain surface Raman enhancement active substrate, wherein, the preset thickness of Ag film of described surface Raman enhancement active substrate is 15nm, and the speed of hot evaporation is
the sample tray slewing rate at described silicon chip place is 20r/min.
Technique scheme has following beneficial effect: because adopt the described method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition to comprise: at the hot evaporation one deck silver of silicon chip surface film; Silicon chip after evaporation silver nanoparticle film is put into chemical vapor deposition CVD reaction chamber and be heated to preset temperature, make described silver-colored film " solid-state dehumidification " to form silver nano-grain; Under described preset temperature, pass into reacting gas, make described silver nano-grain surface uniform silicon growth layer film, form the spherical array structure of core-shell nano; The silicon chip that forms the spherical array structure of core-shell nano is taken out in described CVD reaction chamber, the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtain the technological means of surface Raman enhancement active substrate, so reached following technique effect: (1) preparation is simple, can large area preparation.By hot evaporation and chemical gaseous phase depositing process, can once prepare the active substrate of 2.5cm * 5cm size.And while carrying out Raman detection, only need to be from sample the cleavage sample that goes out 0.5cm * 0.5cm test.Therefore, can once prepare, repeatedly use.(2) the spherical structure of core-shell nano that preparation generates is combined firmly with substrate.Even if ultrasonic or high-temperature heating can not damage structure yet.(3) it is controlled that the SERS substrate of preparing has between nanostructured gap, to the control in gap, can control CVD growth time by controlling annealing time, controls hot evaporation metal film thickness and realize.(4) the SERS substrate of preparing has evenly, reproducible, the advantages such as hypersensitive.Meet the needs of theoretical research and commercial applications.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is a kind of method flow diagram of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition of the embodiment of the present invention.
Fig. 2 is the making schematic flow sheet of application example SERS of the present invention substrate.
Fig. 3 is scanning electron microscope (SEM) figure that the solid-state dehumidification method of application example of the present invention (dewetting) obtains silver nano-grain, and enlargement factor is 50,000 times.
Fig. 4 is the SEM figure of the spherical array structure of core-shell nano that obtains after application example of the present invention chemistry vapor phase deposition, and enlargement factor is 100,000 times.
Fig. 5 is spherical array structure inclination 75 degree of application example core-shell nano of the present invention, amplifies the SEM figure of 100,000 times.
Fig. 6 is the SEM figure that obtains SERS active substrate after the hot evaporation metal silverskin of application example of the present invention, and enlargement factor is 100,000 times.
Fig. 7 is application example SERS active substrate inclination 75 degree of the present invention, amplifies the SEM figure of 100,000 times.
Fig. 8 is atomic force microscope (AFM) figure of application example SERS active substrate of the present invention, and scanning area is 10um.
Fig. 9 is transmission electron microscope (TEM) figure of single core-shell nanospheres shape structure in application example active substrate of the present invention.
Figure 10 is Klarite substrate comparison diagram commercial on the SERS substrate sample of application example optimum of the present invention and market.
Figure 11 is the Mapping collection of illustrative plates of SERS substrate.
Figure 12 detects toluene-ω-thiol (10 in application example SERS of the present invention substrate
-8m) time, the Raman curve obtaining along 10 zoness of different of direction of Figure 11 arrow indication.
Figure 13 detects variable concentrations toluene-ω-thiol (10 in application example SERS of the present invention substrate
-10m～10
-14m) Raman curve map.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
In the recent period, it is the most direct that solid-state dehumidification method (solid-state dewetting) becomes synthetic metal nanoparticle already, effective method.Hot evaporation layer of metal film on smooth substrate, this film is at normal temperatures in steady state (SS).When substrate being heated to uniform temperature (well below the fusing point of metal) and being incubated a period of time, metallic film generation dehumidification (dewetting) in half stable state forms metal nanoparticle, and the thickness of metallic film and the temperature retention time at holding temperature and this temperature are depended in the size of nano particle, interparticle gap.Generally, holding temperature is higher, and temperature retention time is longer, and the particle diameter of the metal nanoparticle of formation is larger, and between nano particle, spacing is also larger.This simple method is prepared SERS active substrate for low-cost, large area provides possibility.But gap, much larger than forming the required optimum distance of " focus " (hot spot), does not have Raman enhancement effect between the metal nanoparticle now obtaining.Therefore, an effective method is exactly the spacing between reduction metal nanoparticle.Utilize chemical vapour deposition technique to deposit uniformly one deck silicon-based nano film on metal nanoparticle (Ag-NPs) surface and gap location, finally form the spherical array structure of core-shell nano.The thickness of silicon-based nano shell is directly proportional to growth time.The formation of silicon-based nano shell, has fixed Nano silver grain on the one hand; Also significantly reduced on the other hand intergranular gap.Now, the spherical array of synthetic core-shell nano does not have Raman enhancement effect, needs again at the certain thickness silver nanoparticle film of silicon nanoshell surface heat evaporation forming, to prepare the active substrate with SERS effect.Finally, by regulating CVD growth time and hot evaporation metal film thickness to realize the active substrate with optimum enhancement effect.
In order to reach above-mentioned technical purpose, as shown in Figure 1, be a kind of method flow diagram of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition of the embodiment of the present invention, the described method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition comprises:
101, at the hot evaporation one deck silver of silicon chip surface film;
102, the silicon chip after evaporation silver nanoparticle film is put into chemical vapor deposition CVD reaction chamber and be heated to preset temperature, make the solid-state dehumidification of described silver-colored film to form silver nano-grain;
103, under described preset temperature, pass into reacting gas, make described silver nano-grain surface uniform silicon growth layer film, form the spherical array structure of core-shell nano;
104, the silicon chip that forms the spherical array structure of core-shell nano is taken out in described CVD reaction chamber, the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtains surface Raman enhancement active substrate.
Preferably, described before the hot evaporation one deck silver of silicon chip surface film, described method can also comprise: the silicon chip of monocrystalline is used to acetone, ethanol, deionized water ultrasonic cleaning successively; Described silicon chip is single-sided polishing, the p-type of doping, N-shaped silicon or unadulterated intrinsic silicon.
Preferably, described monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, can comprise: utilize supersonic cleaning machine, ultrasonic power is 180W, frequency is 40KHz, and monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, and the ultrasonic cleaning time is respectively 10 minutes; Silicon chip after ultrasonic cleaning is put into the concentrated sulphuric acid and the hydrogen peroxide that volume ratio is 4:1 again and soak 15 minutes to remove oxide on surface, by washed with de-ionized water; Finally silicon chip is put into 5% hydrofluorite and soak 5 minutes, make silicon chip surface form Si-H key.
Preferably, described at the hot evaporation one deck silver of silicon chip surface film, can comprise: utilize thermal evaporation coating system at the hot evaporation one deck silver of silicon chip surface film, in hot evaporation chamber, pressure is evacuated to 2.5 * 10
-4pa, the speed of hot evaporation is
the sample tray velocity of rotation at silicon chip place is 20r/min, and the preset thickness of metallic film is 15nm.The advantages such as other plated film mode is compared, and adopts the mode plated film of hot evaporation to have plated film even, and speed is controlled, and preparation is simple, and cost is lower.In general, hot evaporation speed is slower and sample stage rotational speed is more reasonable, and the compactness of metallic film is better, and roughness is lower.
Preferably, the limit heating-up temperature of described reaction cavity is 1050 ℃, is deposited on the silver-colored film of described silicon chip surface in steady state (SS) under room temperature.When cavity being heated in preset temperature process, the silver-colored film in half stable state, in the diffusion of substrate surface generation atom, forms the granule of nanoscale to reduce total free energy.Due to the melt temperature of preset temperature well below metal, while forming nano particle metal in solid-state, the process that Here it is " solid-state dehumidification ".
Preferably, when thickness of metal film one timing, preset temperature is higher, and at this temperature, temperature retention time is longer, and the size of the metallic particles of formation is larger, and between particle, spacing is larger, and particle density is lower.
Preferably, described preset temperature is 540 ℃, and when the sample at described silicon chip place is slowly heated to 540 ℃, described silver-colored film has formed silver nano-grain.The particle diameter major part of the Nano silver grain now obtaining is between 80nm left and right.
Preferably, in described reaction cavity, keep invariablenes pressure of liquid, in heating process, pass into hydrogen to go back the silver oxide of original surface.Pressure is fixed on 10Torr, and the flow of hydrogen is 40SCCM.
Preferably, the described reacting gas passing under described preset temperature can comprise: silane SiH
4with hydrogen H
2; Utilize the sample at described silicon chip place to form on the basis of described silver nano-grain, maintain described preset temperature constant, in reaction chamber, pass into reacting gas, i.e. 5%SiH
4in H
2and the flow that regulates hydrogen is to maintain invariablenes pressure of liquid in chamber, the silicon atom that now under described preset temperature, thermal cracking silane obtains is deposited on the surface of Nano silver grain, makes described silver nano-grain surface uniform silicon growth layer film, forms the spherical array structure of core-shell nano; In above-mentioned course of reaction, reacting gas SiH
4flow be 20sccm, the flow of hydrogen is 20sccm, invariablenes pressure of liquid is at 10Torr, growth time is 90 minutes.Now, along with the particle diameter change of nanosphere is large, the spacing between nanosphere array reduces gradually.Nano level spacing provides necessary condition for surface Raman enhancement active substrate.The thickness of silicon nano thin-film was directly proportional to sample reaction time in reaction chamber.
Preferably, the described silicon chip by the spherical array structure of formation core-shell nano takes out in described CVD reaction chamber, the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtain surface Raman enhancement active substrate, wherein, the preset thickness of Ag film of described surface Raman enhancement active substrate is 15nm, and the speed of hot evaporation is
the sample stage slewing rate at described silicon chip place is 20r/min.The metallic film of different-thickness is different to the enhancing effect of Ramam effect.
Technique scheme has following beneficial effect: because adopt the described method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition to comprise: at the hot evaporation one deck silver of silicon chip surface film; Silicon chip after evaporation silver nanoparticle film is put into chemical vapor deposition CVD reaction chamber and be heated to preset temperature, make described silver-colored film " solid-state dehumidification " to form silver nano-grain; Under described preset temperature, pass into reacting gas, make described silver nano-grain surface uniform silicon growth layer film, form the spherical array structure of core-shell nano; The silicon chip that forms the spherical array structure of core-shell nano is taken out in described CVD reaction chamber, the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtain the technological means of surface Raman enhancement active substrate, so reached following technique effect: this structure nano ball array is combined with substrate firmly and is evenly distributed, preparation is simple, can large area prepare, active substrate has overdelicate Raman and strengthens effect, can detect the organic molecule of lower concentration.
Below in conjunction with application example, the above embodiment of the present invention is elaborated:
Application example one:
This application example provides a kind of method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition, preparation flow schematic diagram as shown in Figure 2, wherein (1) represents hot evaporation layer of metal film on silicon chip, (2) represent substrate heating to anneal, the process of solid-state dehumidification (Dewetting), (3) silver nano-grain obtaining after expression dewetting, (4) represent the process of chemical vapor deposition, (5) the spherical array structure of core-shell nano that expression growth obtains after finishing, (6) represent the process of hot evaporation, (7) represent the SERS active substrate that obtains after hot evaporation one deck silver.
Below technical scheme of the present invention is further described.
Pre-treatment: according to step ultrasonic cleaning 2.5cm * 5cm silicon chip of acetone, ethanol, deionized water, ultrasonic power is 180W, and the ultrasonic cleaning time is respectively 10min.Then the concentrated sulphuric acid that is 98% with massfraction and massfraction are that 30% hydrogen peroxide cleans 15min with oxidation in the mixed liquor of volume ratio 4:1, deionized water rinsing, and nitrogen dries up.It is, in 5% hydrofluoric acid solution, to make silicon chip surface form Si-H key that the silicon chip of processing through hydroxylation is positioned over massfraction.
Hot evaporation metal film: the silicon chip that the surface cleaning up is formed to Si-H key is put into hot evaporated device.When hot evaporation chamber vacuum is evacuated to 2.5 * 10
-4after Pa, slowly strengthen electric current to silver in evaporation boat and be melted into liquid.Now regulate electric current to evaporation rate stabilization to exist
then after regulating sample stage rotating speed 20r/min, open sample baffle plate.Hot evaporation silver film thickness is 15nm.
Preparation nanostructured: the silicon chip of hot evaporation certain thickness silver film is placed in chemical vapor depsotition equipment vacuum cavity, cavity is evacuated to 9 * 10
-7torr, after pass into high pure nitrogen to chamber pressure and be stabilized in 10Torr.Now, starting cavity slowly to heat and keep passing into hydrogen flowing quantity is 40sccm.When temperature is slowly increased to 540 while spending, silver film has formed silver nano-grain, as shown in Figure 3, be scanning electron microscope (SEM) figure that the solid-state dehumidification method of application example of the present invention (dewetting) obtains silver nano-grain, enlargement factor is 50,000 times.At this temperature, pass into reactant gas silane more subsequently, flow control is at 20sccm, and in silane, cracking silicon atom out starts in substrate surface deposition, is the coated one deck silverskin in silver nano-grain surface.The core-shell nano structure that growth obtains after 90min is as Fig. 4, and Fig. 5: Fig. 4 is the SEM figure of the spherical array structure of core-shell nano that obtains after application example chemistry vapor phase deposition of the present invention, and enlargement factor is 100,000 times.Fig. 5 is spherical array structure inclination 75 degree of application example core-shell nano of the present invention, amplifies the SEM figure of 100,000 times.
Active SERS substrate preparation: the nucleocapsid structure obtaining after gas-phase reaction does not have Raman enhancement effect, also need to be at surface coverage layer of metal film.Therefore, the sample after growth is finished takes out and is reapposed on hot evaporation cavity sample tray evaporation one deck silver film again.Technological parameter is with above-mentioned consistent, evaporation speed
the Raman signal that evaporation thickness obtains while being 15nm is the strongest, SEM as Fig. 6-Fig. 9: Fig. 6 be the SEM figure that obtains SERS active substrate after the hot evaporation metal silverskin of application example of the present invention, enlargement factor is 100,000 times.Fig. 7 is application example SERS active substrate inclination 75 degree of the present invention, amplifies the SEM figure of 100,000 times.Fig. 8 is atomic force microscope (AFM) figure of application example SERS active substrate of the present invention, and scanning area is 10um.Fig. 9 is transmission electron microscope (TEM) figure of single core-shell nanospheres shape structure in application example active substrate of the present invention.
Figure 10 is Klarite substrate comparison diagram commercial on the SERS substrate sample of application example optimum of the present invention and market.The ethanolic solution concentration of toluene-ω-thiol is 4 * 10
-4m, sample Critical time is 1 hour.Figure 11 is the Mapping collection of illustrative plates of SERS substrate.This collection of illustrative plates is 100 sites that obtain every 100 micron pitch on 10 * 10 grid, gathers respectively p-thiocresol Raman signal on different sites.Highest peak 1076cm
-1locating curve that corresponding signal intensity plots can be similar to a series of level line and distribute.The relative standard deviation (RSD) corresponding to homogeneity of the substrate obtaining from Mapping collection of illustrative plates is 7.94%.Figure 12 detects toluene-ω-thiol (10 in application example SERS of the present invention substrate
-8m) time, the Raman curve obtaining along 10 zoness of different of direction of Figure 11 arrow indication.What Figure 12 was corresponding is the horizontal arrow of Figure 11, represents that along continuous straight runs is every 100 microns of 10 points getting, and 10 Raman curves that obtain, are used for illustrating homogeneity.Figure 13 detects variable concentrations toluene-ω-thiol (10 in application example SERS of the present invention substrate
-10m～10
-14m) Raman curve map.
Application example two:
This application example provides a kind of method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition, preparation flow schematic diagram as shown in Figure 2, wherein (1) represents hot evaporation layer of metal film on silicon chip, (2) represent substrate heating to anneal, the process of solid-state dehumidification (Dewetting), (3) silver nano-grain obtaining after expression dewetting, (4) represent the process of chemical vapor deposition, (5) the spherical array structure of core-shell nano that expression growth obtains after finishing, (6) represent the process of hot evaporation, (7) represent the SERS active substrate that obtains after hot evaporation layer of gold.
Below technical scheme of the present invention is further described.
Pre-treatment: according to step ultrasonic cleaning 2.5cm * 5cm silicon chip of acetone, ethanol, deionized water, ultrasonic power is 180W, and the ultrasonic cleaning time is respectively 10min.Then the concentrated sulphuric acid that is 98% with massfraction and massfraction are that 30% hydrogen peroxide cleans 15min with oxidation in the mixed liquor of volume ratio 4:1, deionized water rinsing, and nitrogen dries up.It is, in 5% hydrofluoric acid solution, to make silicon chip surface form Si-H key that the silicon chip of processing through hydroxylation is positioned over massfraction.
Hot evaporation metal film: the silicon chip that the surface cleaning up is formed to Si-H key is put into hot evaporated device.When hot evaporation chamber vacuum is evacuated to 2.5 * 10
-4after Pa, slowly strengthen electric current to silver in evaporation boat and be melted into liquid.Now regulate electric current to evaporation rate stabilization to exist
then after regulating sample tray rotating speed 20r/min, open sample baffle plate.Hot evaporation silver film thickness is 15nm.
Preparation nanostructured: the silicon chip of hot evaporation certain thickness silver film is placed in chemical vapor depsotition equipment vacuum cavity, cavity is evacuated to 9 * 10
-7torr, after pass into high pure nitrogen to chamber pressure and be stabilized in 10Torr.Now, starting cavity slowly to heat and keep passing into hydrogen flowing quantity is 40sccm.When temperature is slowly increased to 540 ℃, silver film has formed silver nano-grain, as shown in Figure 3, be scanning electron microscope (SEM) figure that the solid-state dehumidification method of application example of the present invention (dewetting) obtains silver nano-grain, enlargement factor is 50,000 times.At this temperature, pass into reactant gas silane more subsequently, flow control is at 20sccm, and in silane, cracking silicon atom out starts in substrate surface deposition, is the coated one deck silverskin in silver nano-grain surface.The core-shell nano structure that growth obtains after 90min is as Fig. 4, and Fig. 5: Fig. 4 is the SEM figure of the spherical array structure of core-shell nano that obtains after application example chemistry vapor phase deposition of the present invention, and enlargement factor is 100,000 times.Fig. 5 is spherical array structure inclination 75 degree of application example core-shell nano of the present invention, amplifies the SEM figure of 100,000 times.
Active SERS substrate preparation: the nucleocapsid structure obtaining after gas-phase reaction does not have Raman enhancement effect, also need to be at surface coverage layer of metal film.Therefore, the sample after growth is finished takes out and is reapposed on hot evaporation cavity sample stage evaporation layer of gold film again.Technological parameter is with above-mentioned consistent, evaporation speed
other explanation and accompanying drawings in above-mentioned application example one are similar, do not repeat them here.
This structure nano ball array that above-mentioned application example obtains is combined with substrate firmly and is evenly distributed, and preparation is simple, can large area prepare, and active substrate has overdelicate Raman and strengthens effect, can detect the organic molecule of lower concentration.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only the specific embodiment of the present invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. based on chemical vapor deposition, prepare a method for surperficial Raman enhanced activity substrate, it is characterized in that, the described method of preparing the substrate of surperficial Raman enhanced activity based on chemical vapor deposition comprises:
At the hot evaporation one deck silver of silicon chip surface film;
Silicon chip after evaporation silver nanoparticle film is put into chemical vapor deposition CVD reaction chamber and be heated to preset temperature, make the solid-state dehumidification of described silver-colored film to form silver nano-grain;
Under described preset temperature, pass into reacting gas, make described silver nano-grain surface uniform silicon growth layer film, form the spherical array structure of core-shell nano;
The silicon chip that forms the spherical array structure of core-shell nano is taken out in described CVD reaction chamber, and the silverskin of the preset thickness of hot evaporation again on the surface of the spherical array structure of described core-shell nano, obtains surface Raman enhancement active substrate.
2. based on chemical vapor deposition, prepare as claimed in claim 1 the method for surperficial Raman enhanced activity substrate, it is characterized in that, described before the hot evaporation one deck silver of silicon chip surface film, described method also comprises:
The silicon chip of monocrystalline is used to acetone, ethanol, deionized water ultrasonic cleaning successively; Described silicon chip is single-sided polishing, the p-type of doping, N-shaped monocrystalline silicon piece or unadulterated intrinsic silicon chip.
3. based on chemical vapor deposition, prepare as claimed in claim 2 the method for surperficial Raman enhanced activity substrate, it is characterized in that, described monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, comprising:
Utilize supersonic cleaning machine, ultrasonic power is 180W, and frequency is 40KHz, and monocrystalline silicon piece is used to acetone, ethanol, deionized water ultrasonic cleaning successively, and the ultrasonic cleaning time is respectively 10 minutes;
Silicon chip after ultrasonic cleaning is put into the concentrated sulphuric acid and the hydrogen peroxide that volume ratio is 4:1 again and soak 15 minutes to remove oxide on surface, by washed with de-ionized water;
Finally silicon chip is put into 5% hydrofluorite and soak 5 minutes, make silicon chip surface form Si-H key.
4. based on chemical vapor deposition, prepare as claimed in claim 1 the method for surperficial Raman enhanced activity substrate, it is characterized in that, described at the hot evaporation one deck silver of silicon chip surface film, comprising:
Utilize thermal evaporation coating system at the hot evaporation one deck silver of silicon chip surface film, in hot evaporation chamber, pressure is evacuated to 2.5 * 10
-4pa, the speed of hot evaporation is
the sample tray velocity of rotation at silicon chip place is 20r/min, and the thickness of metallic film is 15nm.
5. based on chemical vapor deposition, prepare as claimed in claim 1 the method for surperficial Raman enhanced activity substrate, it is characterized in that,
The limit heating-up temperature of described reaction cavity is 1050 ℃, is deposited on the silver-colored film of described silicon chip surface in steady state (SS) under room temperature.
6. based on chemical vapor deposition, prepare as claimed in claim 5 the method for surperficial Raman enhanced activity substrate, it is characterized in that,
When thickness of metal film one timing, preset temperature is higher, and at this temperature, temperature retention time is longer, and the size of the metallic particles of formation is larger, and between particle, spacing is larger, and particle density is lower.
7. based on chemical vapor deposition, prepare as claimed in claim 5 the method for surperficial Raman enhanced activity substrate, it is characterized in that,
Described preset temperature is 540 ℃, and when the sample at described silicon chip place is heated to 540 ℃ in 30 minutes, described silver-colored film has formed silver nano-grain.
8. based on chemical vapor deposition, prepare as claimed in claim 5 the method for surperficial Raman enhanced activity substrate, it is characterized in that,
In described reaction cavity, keep invariablenes pressure of liquid, in heating process, pass into hydrogen to go back the silver oxide of original surface.Pressure is fixed on 10Torr, and the flow of hydrogen is 40sccm.
9. based on chemical vapor deposition, prepare as claimed in claim 1 the method for surperficial Raman enhanced activity substrate, it is characterized in that, the described reacting gas passing under described preset temperature comprises: silane SiH
4with hydrogen H
2;
Utilize the sample at described silicon chip place to form on the basis of described silver nano-grain, maintain described preset temperature constant, in reaction chamber, pass into reacting gas, i.e. 5%SiH
4in H
2and the flow that regulates hydrogen is to maintain invariablenes pressure of liquid in chamber, the silicon atom that now under described preset temperature, thermal cracking silane obtains is deposited on the surface of Nano silver grain, makes described silver nano-grain surface uniform silicon growth layer film, forms the spherical array structure of core-shell nano; In above-mentioned course of reaction, reacting gas SiH
4flow be 20sccm, the flow of hydrogen is 20sccm, invariablenes pressure of liquid is at 10Torr, growth time is 90 minutes.
10. based on chemical vapor deposition, prepare as claimed in claim 1 the method for surperficial Raman enhanced activity substrate, it is characterized in that,
The described silicon chip by the spherical array structure of formation core-shell nano takes out in described CVD reaction chamber, by thermal evaporation coating system on the surface of the spherical array structure of described core-shell nano the silverskin of the preset thickness of hot evaporation again, obtain surface Raman enhancement active substrate, wherein, the preset thickness of Ag film of described surface Raman enhancement active substrate is 15nm, and the speed of hot evaporation is
the sample tray slewing rate at described silicon chip place is 20r/min.
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